Synthesis and characterization of 4-chlorobutyl ester of 5-(8-carboxyl-1-naphthyl)-10,15,20-triphenyl-porphyrin and its zinc complex

Article abstract of DOI:10.1080/15533174.2016.1212214

In the presence of Br?nsted–Lowry acids (phenol or dry HCl), the acyl chloride, which was obtained by the reaction between 5-(8-carboxyl-1-naphthyl)-10,15,20-triphenyl-porphyrin (CNTPP) and oxalyl chloride, reacted with tetrahydrofuran and led to the 4-chlorobutyl ester, P1, as the result of the acylative cleavage. P1 and its zinc complex [ZnP1] have been characterized by¹H NMR. The structure of [ZnP1] was obtained by X-ray crystallography. Zinc is coordinated by four pyrrole nitrogens. The 8-position substituent, a 4- chlorobutyl ester group, lies above the porphyrin plane.

Full text of DOI:10.1080/15533174.2016.1212214

Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry
ISSN: 1553-3174 (Print) 1553-3182 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt20
Synthesis and Characterization of 4-Chlorobutyl
Ester of 5-(8-Carboxyl-1-naphthyl)-10,15,20-
triphenyl-porphyrin and its Zinc Complex
Huan Liu, Caifen Ou, Ben Ma & Chuanjiang Hu
To cite this article: Huan Liu, Caifen Ou, Ben Ma & Chuanjiang Hu (2016): Synthesis and
Characterization of 4-Chlorobutyl Ester of 5-(8-Carboxyl-1-naphthyl)-10,15,20-triphenyl-
porphyrin and its Zinc Complex, Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry, DOI: 10.1080/15533174.2016.1212214
To link to this article: http://dx.doi.org/10.1080/15533174.2016.1212214
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ACCEPTED MANUSCRIPT
Synthesis and Characterization of 4-Chlorobutyl Ester of
-(8-Carboxyl-1-naphthyl)-10,15,20-triphenyl-porphyrin and its Zinc Complex
Huan Liu,† Caifen Ou,† Ben Ma, Chuanjiang Hu*
5
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical
Engineering and Materials Science, Soochow University, Suzhou 215123, P.R. China
In the presence of Brønsted–Lowry acids (phenol or dry HCl), the acyl chloride, which was
obtained by the reaction between 5-(8-carboxyl-1-naphthyl) -10,15,20-triphenyl-porphyrin
(
CNTPP) and oxalyl chloride, reacted with tetrahydrofuran and led to the 4-chlorobutyl ester, P1,
as the result of the acylative cleavage. P1 and its zinc complex [ZnP1] have been characterized
1
by H NMR. The structure of [ZnP1] was obtained by X-ray crystallography. Zinc is coordinated
by four pyrrole nitrogens. The 8-position substituent, a 4-chlorobutyl ester group, lies above the
porphyrin plane.
Keywords
chlorobutyl; porphyrin; acylative cleavage; tetrahydrofuran; acid.
*
Corresponding author. E-mail: cjhu@suda.edu.cn.
†
These authors contribute equally.
1
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1
. Introduction
Porphyrins and their derivatives have been found in many biological systems, such as
hemoglobin, cytochrome P450, horseradish peroxidase, etc. Besides their importance in
biological sciences, porphyrins have also play important roles in material sciences, such as
[
1-5]
catalytic asymmetric synthesis, nonlinear optics, molecular devices, etc.
One attracting
feature of the porphyrin species is that it can be functionalized at many positions, such as meso
or  positions, which can lead to many kind of novel porphyrins with various structures and
functions.
[
6-11]
We have recently been working on a series of mononaphthyl substituted porphyrins.
These porphyrins can be easily functionalized at the 8-position of the naphthyl group. For
example, we have designed and synthesized its phenolate derivative with a covalently attached
phenol tail, the ligand P3 (shown in Scheme 1), as a structural mimic of catalases, which has a
[8]
hanged phenol group at the appropriate position to further interact with the center metal. In that
preparation, dichloromethane was used as the solvent. When we extended it to other phenols, we
tried to use tetrahydrofuran (THF) as the solvent. Interestingly, the 4-chlorobutyl ester, P1, has
been obtained as the major product as shown in Scheme 1. Its zinc complex was also prepared
and crystallographically characterized. Herein, we report the synthesis and characterization of P1
and [ZnP1].
2
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2
2
2
. Experimental Section
.1. General procedures
.1.1. Materials and General Methods. All reagents were obtained from commercial sources
without further purification unless otherwise noted. Anhydrous tetrahydrofuran (THF) was dried
and redistilled over sodium benzophenone ketyl. The dichloromethane (CH Cl ) was freshly
distilled from CaH under nitrogen used. CNTPP was synthesized according to the reported
H NMR spectra were carried out using a Bruker AVANCE 400 spectrometer in
. Mass spectra were taken with Agilent 6220 Accurate-Mass TOF LC/MS. UV-vis spectra
2
2
2
[10] 1
method.
CDCl
3
were measured with a Shimadzu UV-3150 spectrometer. IR spectra were measured with a
Bruker vertex-70 spectrometer. The single crystal structure was measured with Agilent Xcalibur
diffractometer with an Atlas (Gemini Ultra Cu) detector. Elemental analyses (C, H and N) were
performed with an Elementar Vario EL III analytical instrument.
2
2
.2. Synthesis
.2.1. Synthesis of compound P1, P2, P3, P4, P5
5
-(8-carboxyl-1-naphthyl)-10, 15, 20-triphenyl-porphyrinate (CNTPP) (0.20 g, 0.28 mmol)
was dissolved in dichloromethane (20 mL). Oxalyl chloride (4.0 mL, 42 mmol) was slowly
added to the above solution and stirred for 2 h under N . The excess reagent was removed under
reduced pressure. The residue was redissolved in anhydrous THF. The corresponding phenol
2
(
phenol for P2, catechol for P3, m-dihydroxybenzene for P4, hydroquinone for P5, 60 equiv.)
3
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was added to the solution and stirred for 16 h. The solution was rotor evaporated to dryness
under vacuum. The red solid was purified by silicon chromatography, eluted with
CH
2
Cl /petroleum ether (1:1). For phenol, P1, yield 69%; P2, yield 16%. For catechol, P1, yield
2
8
2%; P3, yield 12%. For m-dihydroxybenzene, P1, yield 76%, P4, yield 15%. For hydroquinone,
P1, yield 73%; P5, yield 14%.
1
P1, H NMR (400 MHz, CDCl
3
):  8.85 (s, 4H), 8.77 (d, 2H), 8.63 (d, 2H), 8.33 (t, 4H), 8.25
(
t, 3H), 8.10 (d, 2H), 7.90 (t, 1H), 7.76 (m, 9H), 7.56 (t, 1H), 7.32 (d, 1H), 2.16 (t, 2H), 0.33 (s,
-1
-1
2
H), -0.08 (s, 2H), -0.58 (m, 2H), -2.67 (s, 2H). UV-Vis (CH
2
Cl ): max, nm (, M cm ): 421
2
5
4
3
3
3
(
5.45 × 10 ), 518 (2.17 × 10 ), 553 (8.67 × 10 ), 592 (6.55 × 10 ), 649 (3.84 × 10 ). IR(KBr):
-1
v,cm 3431 (m), 3316 (m), 3053 (m), 2953 (m), 1716 (s), 1596 (m), 1558 (m), 1473 (s), 1440
(
m), 1363 (s), 1347 (s), 1194 (s), 1175 (m), 973 (s), 801 (s), 775 (s), 730 (s), 515 (w).
+
LC-ESI-MS: m/z calcd for C53
H39ClN
4
O
2
798.28; found 799.28 [M+H] . Anal. Calc.
C
53
H
39ClN
4
O
2
2.0CH
2
Cl
2
: C, 68.16; H, 4.47; N, 5.78%. Found: C, 68.45; H, 4.36; N, 5.89%.
):  8.85 (d, 2H), 8.81 (d, 2H), 8.69 (d, 2H), 8.66 (s, 2H), 8.48
1
P2, H NMR (400 MHz, CDCl
3
(
(
(
d, 1H), 8.33 (m , 4H), 8.12 (d, 4H), 7.95 (t, 1H), 7.80 (s, 3H), 7.72 (m, 6H), 7.61 (m, 2H), 5.61
-1
-1
t, 1H), 4.77 (t, 2H), 3.67 (d, 2H), -2.60 (s, 2H). UV-Vis (CH
2
Cl ): max, nm (, M cm ): 423
2
5
4
3
3
3
5.45 × 10 ), 519 (2.24 × 10 ), 555 (9.61 × 10 ), 594 (6.82 × 10 ), 649(3.95 × 10 ). IR(KBr):
-1
v,cm 3312 (m), 3052 (m), 1739 (s), 1594 (m), 1558 (m), 1490 (s), 1473 (m), 1440 (m), 1184 (s),
9
63 (s), 801 (s), 729 (s), 699 (s). LC-ESI-MS: m/z calcd for C55
H
36
N
4
2
O 784.28; found 807.27
4
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+
[
M+Na] . Anal. Calc. C55
H
36
N
4
O
2
1.0CH
2
Cl : C, 77.33; H, 4.40; N, 6.44%. Found: C, 78.97; H,
2
4
.36; N, 6.55%.
1
P3, H NMR (400 MHz, CDCl
3
):  8.82 (d, 2H), 8.78 (d, 2H), 8.68 (d, 2H), 8.61 (d, 2H), 8.46
(
d, 1H), 8.36 (d, 1H), 8.33 (d, 1H), 8.25 (d, 2H), 8.16 (d, 2H), 8.09 (d, 2H), 7.96 (t, 1H), 7.79 (s,
H), 7.72 (m, 6H), 7.62 (t, 1H), 7.55 (d, 1H), 5.43 (m, 2H), 3.41 (t, 1H), 2.54 (d, 1H). UV-Vis
3
-1
-1
5
4
3
(
CH
2
Cl ): max, nm (, M cm ): 422 (5.51 × 10 ), 519 (2.14 × 10 ), 555 (1.00 × 10 ), 594 (6.34
2
3
3
-1
×
10 ), 649 (3.62 × 10 ). IR(KBr): v,cm 3416 (m), 3314 (m), 3051 (m), 2952 (m), 1740 (m),
1
7
596 (m), 1492 (m), 1472 (m), 1459 (m), 1440 (m), 1265 (s), 1174 (s), 964 (s), 800 (s), 729 (s),
+
00 (s), 558 (w). LC-ESI-MS: m/z calcd for C55
H
36
N
4
O
3
800.28; found 801.29 [M+H] . Anal.
Calcd for C55
H
36
N
4
O
3
0.7CH
2
Cl
2
: C, 77.76; H, 4.38; N, 6.51. Found: C, 77.54; H, 4.36; N, 6.48.
):  8.90 (d, 2H), 8.86 (d, 2H), 8.73 (d, 2H), 8.66 (s, 2H), 8.57
1
P4, H NMR (400 MHz, CDCl
3
(
d, 1H), 8.37 (m , 1H), 8.29 (m, 3H), 8.17 (d, 2H), 8.12 (d, 2H), 7.98 (t, 1H), 7.80 (s, 3H), 7.72
m, 6H), 7.61 (t, 1H), 7.54 (d, 1H), 5.92 (t, 1H) , 5.19 (d, 1H), 5.07 (d, 1H), 0.06 (s, 1H), -0.56 (s,
(
-
1
-1
5
4
1
5
H) , -2.68. (s, 2H). UV-Vis (CH
2
Cl ): max, nm (, M cm ): 423 (3.94 × 10 ), 519 (1.32 × 10 ),
2
4
3
3
-1
55 (4.18 × 10 ), 594 (3.12 × 10 ), 649 (2.62 × 10 ). IR(KBr): v,cm 3317 (m), 3052 (m), 2921
(
m), 1739 (m), 1595 (m), 1473 (m), 1440 (m), 1347 (m), 1263 (m), 1184 (s), 1139 (s), 964 (m),
7
99 (s), 729 (s), 701 (s), 661 (w). LC-ESI-MS: m/z calcd for C55
H
36
N
4
3
O 800.28; found 823.27
+
[
M+Na] . Anal. Calc. C55
H
36
N
4
O
3
0.4CH
2
Cl
2
: C, 79.70; H, 4.44; N, 6.71%. Found: C, 79.95; H,
4
.32; N, 6.69%.
5
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1
P5, H NMR (400 MHz, CDCl
3
):  8.82 (d, 2H), 8.79 (d, 2H), 8.66 (d, 2H), 8.61 (s, 2H), 8.44
(
(
(
d, 1H), 8.35 (m , 2H), 8.24 (s, 2H), 8.11 (m, 4H), 7.94 (t, 1H), 7.72 (m, 9H), 7.61 (t, 1H), 7.54
-1
-1
d, 1H), 3.86 (d, 2H), 3.34 (t, 3H), -2.69 (s, 2H). UV-Vis (CH
2
Cl ): max, nm (, M cm ): 423
2
5
4
3
3
3
4.06 × 10 ), 519 (1.67 × 10 ), 555 (7.39 × 10 ), 594 (5.17 × 10 ), 649 (3.5 × 10 ). IR(KBr):
-1
v,cm 3385 (m), 3315 (m), 3051 (m), 2921 (m), 1737 (m), 1707 (m), 1596 (m), 1503 (s), 1472
(
(
m), 1439 (m), 1347 (m), 1264 (m), 1175 (s), 1137 (m), 970 (m), 799 (s), 729 (s), 700 (s), 519
+
w). LC-ESI-MS: m/z calcd for C55
0.4CH Cl
H
36
N
4
O
3
800.28; found 823.27 [M+Na] . Anal. Calc.
C
55
H
36
N
4
O
3
2
2
: C, 79.70; H, 4.44; N, 6.71%. Found: C, 79.84; H, 4.39; N, 6.59%.
2
.2.2. Synthesis of compound B1, B2
Benzoyl chloride (110 μL, 0.91 mmol) was dissolved in anhydrous THF (30 mL) in Schlenk
flask, and catechol (2.0 g, 18 mmol，20 equiv.) was added under N
2
. After 48 h, the reaction
was complete. The excess THF was rotor evaporated to dryness under vacuum. The light yellow
liquid B1 and B2 obtained by chromatography (silica, CH
2
Cl
2
/petroleum ether 1 : 4).
1
For B1, yield (0.14 g, 73%). H NMR (400 MHz, CDCl
3
):  8.03 (d, 2H), 7.57 (t, 1H), 7.45 (t,
-
1
-1
2
H), 4.37 (t, 2H), 3.62 (t, 2H), 1.95 (m , 4H). UV-Vis (CH
2
Cl
10 ). IR(KBr): v,cm 3421 (m), 2959 (s), 1719 (s), 1601 (w), 1451 (s), 1314 (s), 1274 (s), 1176
212.06; found
2
): max, nm (, M cm ): 234 (1.1
4
-1
×
(
m), 1115 (s), 1070 (s), 1026 (m), 711 (s). LC-ESI-MS:m/z calcd for C11
H
13ClO
2
+
2
6
35.05 [M+Na] . Anal. Calc. C11
H13ClO
2
0.5H
2
O: C, 59.60; H, 6.37%. Found: C, 60.10; H,
.41%.
6
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1
For B2, yield (0.026 g, 13%). H NMR (400 MHz, CDCl
3
):  8.22 (d, 2H), 7.67 (t, 1H), 7.54
Cl
M cm ): 234 (1.7 × 10 ). IR(KBr): v,cm 3412 (s), 1716 (s), 1614 (m), 1596 (s), 1511 (s), 1460
(
t, 2H), 7.18 (t, 2H), 7.07 (d, 1H), 6.98 (t , 1H), 5.62 (s, 1H). UV-Vis (CH
2
2
): max, nm (,
-
1
-1
4
-1
(
s), 1346 (s), 1297 (s), 1272 (s), 1229 (s), 1175 (s), 1098 (s), 1068 (s), 753 (s), 712 (s), 557 (w).
+
LC-ESI-MS: m/z calcd for C13
H
10
O
3
214.06; found 237.05 [M+Na] . Anal. Calc.
C
13
H
10
O
3
0.1H O: C, 72.28; H, 4.76%. Found: C, 71.81; H, 4.53%.
2
2
.2.3. Synthesis of compound B1 or P1 by using dry HCl.
Similar to the previous reactions, instead of phenol, dry HCl gas was passed through the
solution for 10 mins. For P1, yield 91%; For B1, yield 93%.
.2.4. Synthesis of [ZnP1]
A solution of Zn(CH COO) ·2H O (0.125 g, 0.57 mmol) in methanol (5 mL) was added to the
2
3
2
2
solution of P1 (0.22 g, 0.28 mmol) in chloroform (50 mL). The mixture was refluxed for three
hours. After the completion of the reaction, the solution was washed with water (3×100 mL). The
organic layer was collected, then dried over magnesium sulfate, and concentrated under reduced
pressure. The residue was purified by chromatography (silica, CH
2
Cl
2
/hexane 1:1). The light
):  8.93 (t, 4H), 8.85
1
purple solid was obtained. Yield 0.20 g (82%). H NMR (400 MHz, CDCl
3
(
(
d, 2H), 8.70 (d, 2H), 8.29 (m, 7H) , 8.12 (d , 2H), 7.90 (t, 1H), 7.76 (m, 9H), 7.56 (t, 1H), 7.28
d, 1H), 2.66 (t, 2H), 0.64 (t, 2H), 0.52 (m, 2H), 0.10 (m, 2H). UV-Vis (CH Cl ): max, nm (,
2
2
-1
-1
5
4
3
-1
M cm ): 423 (6.39 × 10 ), 551 (2.55 × 10 ), 592 (4.64 × 10 ). IR(KBr): v,cm 3420 (m), 3052
7
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(
(
[
m), 2951 (m), 1718 (s), 1595 (m), 1485 (m), 1439 (m), 1338 (s), 1205 (s), 1067 (m), 1003
s),798 (s), 700 (s), 664 (w). LC-ESI-MS: m/z calcd for ZnC53
H37ClN
4
2
O 860.19; found 861.20
+
M+H] . Anal. Calc. C53
H39ClN
4
O
2
0.5CH
2
Cl : C, 70.99; H, 4.23; N, 6.19%. Found: C, 71.29;
2
H, 4.35; N, 6.28%.
.3. X-ray crystallography
2
Single crystals of [ZnP1] were obtained by slow evaporation of its solution in the mixture of
dichloromethane and hexane (1:1). All measurements were made on Agilent Xcalibur
diffractometer with an Atlas (Gemini Ultra Cu) detector by using graphite monochromated Cu
3
Ka (λ = 0.154178 nm). A purple crystal with the dimensions 0.35 x 0.30 x 0.20 mm was used for
the structure determination. It was glued to a glass fiber by epoxy cement and measured at 223 K.
Cell refinement and data reduction were carried out with the use of the program CrysAlisPro
(
Agilent Technologies, Version 1.171.36.32, 2013), and absorption corrections (multi-scan) were
2
applied. The structure was solved by direct methods using SHELXS-97 and refined against F
[
12]
using SHELXL-97;
subsequent difference Fourier syntheses led to the location of the
remaining nonhydrogen atoms. For the structure refinement all data were used including negative
intensities. The asymmetric unit contains one porphyrin molecule and one methylene chloride
solvate. All nonhydrogen atoms were refined anisotropically. Hydrogen atoms were added with
the standard SHELXL-97 idealization methods. Brief crystal data for the structure are listed in
Table 1.
8
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3
. Results and Discussion
The compound P1 has been synthesized in anaerobic condition, the overall procedure is
summarized in Scheme 1. Our original design is to synthesize P2-P5. Unexpectedly, the reaction
led directly to the production of P1, a 4-chlorobutyl ester, as the major product; P2 (or P3, P4,
P5) as the minor product. Their formulae have been confirmed by electrospary-ionization (ESI)
mass spectrometry (shown in the supporting information). For example, ESI revealed the ion
+
peaks at m/z = 799.28 for the compound P1, which corresponds to [M+H] .
In the reaction shown in Scheme 1, the butyl group was obviously from THF, the product P1
was formed by the cleavage of tetrahydrofuran. The cleavage of THF with acyl chlorides is a
useful reaction, particularly in the synthesis of molecules where a four-carbon chain is required
[
13-15]
to be added.
reaction. So phenol, a Brønsted–Lowry acid, could be the key reagent to promote the cleavage.
We also tried to add NEt during the reaction, no P1 was obtained under such condition. It
Besides the acyl chloride, phenol is the other possible reagent involving in the
3
confirms the acidity of phenol is essential to the acylative cleavage of tetrahydrofuran. Since
phenols are weak Brønsted–Lowry acids, how about strong Brønsted–Lowry acid? We also tried
to use dry HCl as shown in Scheme 2. The reaction led to a higher yield of P1 (91%).
Furthermore, comparison experiments have been performed to benzoic chloride instead of
CNTPP. As shown in Scheme 2, in the presence of excess catechol, the reaction ii led to both B1
(
4-chlorobutyl ester) and B2. When dry HCl was used, the reaction iii gave B1 as the only
9
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product. The above study suggests such acylative cleavage reaction is Brønsted–Lowry
acid-promoted.
As we also learned from literatures that many catalysts have been reported for similar
[
16]
[17]
[18]
[19]
transformation. There are metallic complexes, such as ZnCl2,
FeCl3,
MoCl5,
InBr3,
[20]
[21]
3,
[22]
[23]
[24]
BiCl
3
and La(NO
3
)
or metals, such as Al,
Zn
and Mg,
or nonmetals, such as
[
25]
[26]
iodine and graphite. In most cases, they are Lewis acids. So it may not be too surprising in
light of the results from analogous reactions using Brønsted–Lowry acids. The detailed reaction
mechanism is not clear so far. It is likely that a tetrahydrofuran molecule is broken down, and
subsequently forms a chlorobutyl ester with the 8-carboxyl-naphthyl group since it is known that
THF is unstable under acidic condition, and can react with HCl to produce 4-chlorobutanol under
[27]
certain conditions.
1
3
.1. H NMR Spectra
Due to the ring current effect, NMR spectroscopy is a good method to study intramolecular
[28]
1
interactions in porphyrins.
All these compounds have been characterized by H NMR. For
1
comparison, 4-chlorobutyl benzoate (compound B1) has been prepared. H NMR spectra of P1,
1
B1 and [ZnP1] are shown in Fig. 1. The corresponding chemical shifts for H NMR are listed in
Table S1 in the supporting information. For P1, the signal at -2.67 ppm has been assigned to two
[28]
inner NH protons, which is typical in free base porphyrin. The signals of four protons at -0.58,
-
0.08, 0.33, 2.16 ppm are assigned to the butyl group. The corresponding resonances for the
10
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[29]
compound B1 are located at 4.35 (H2), 1.95 (H3 and H4) and 3.59 (H5) according to literature.
If we consider that the butyl group is located above the porphyrin plane in the crystal structure
vide infra), the porphyrin ring current effect will cause their resonances shift upfield. So these
(
signals are assigned as shown in Figure 1. Their corresponding upfield shifts are 4.01, 2.51, 2.02
and 1.42 ppm comparing with compound B1. Such upfield shifts are similar to the case of
[
6]
5
-(8-ethoxycarbonyl-1-naphthyl) -10,15,20-triphenyl porphyrin (ENTPP). For [ZnP1], the
resonances of butyl group have slight downfield shifts comparing with the compound P1. We
notice there is one resonance at 1.20 ppm, which is caused by the residue H O in CDCl . It is
generally at 1.50 ppm. The upfield shift for H O indicates the water molecule is coordinated to
the zinc porphyrinate. As in our previous report on [Zn(ENTPP)(H
suggests H O is coordinated to zinc through the same side of the ester group. In our case, such
coordination of H
2
3
2
[7]
2
O), the crystal structure
2
2
O could cause the butyl group away from the porphyrin plane, therefore lead
1
to slightly downfield shifts of their H NMR resonances.
3
.2. Molecular Structure
One of the single crystals of [ZnP1] was measured by X-ray crystallography. Its structure was
resolved in the space group P2 /c. One asymmetric unit contains one complete porphyrin and
1
one methylene chloride solvate. The structure of porphyrin is displayed in Fig. 2. It has one
naphthyl and three phenyl groups on the meso-position. Zinc was inserted into the porphyrin
core, and was coordinated by four pyrrole nitrogens. It is coplanar with four nitrogen (the
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displacement out of four nitrogen plane is 0.03 Å), which is typical for four-coordinate species.
The porphyrin core is quite planar with the maximum deviation of 24 atoms from the mean plane
as 0.12 Ǻ (see Figure 3). Selected bond distances are listed in Table 2. The average Zn—N
p
[
7]
distance is 2.035(6) Ǻ, which is slightly shorter than that in five-coordinate zinc complexes.
Because of the constraint of naphthyl unit, the 8-position substituents, a chlorobutyl group, lies
above the porphyrin plane (vide supra). The distances between C(2), C(3), C(4), C(5) and the
porphyrin plane are 3.42, 3.56, 4.56 and 4.58 Ǻ, respectively.
4
. Conclusion
In conclusion, the 4-chlorobutyl ester of CNTPP was synthesized. Its structure was
1
confirmed by mass spectroscopy, H NMR and X-ray crystallography. Such a product was
formed by the acylative cleavage of tetrahydrofuran. Our study suggests the cleavage is
promoted by Brønsted–Lowry acids. It provides a convenient method to prepare P1, a
4
-chlorobutyl derivative of porphyrin with a four-carbon chain. Such a compound could also be
used as a precursor for other derivatives of CNTPP.
Acknowledgment
This work was supported by the Natural Science Foundation of China (No. 20971093 and
2
1271133), and the Priority Academic Program Development of Jiangsu Higher Education
Institutions.
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Supplementary material
1
Supplemental data is available at the publisher’s website. Mass spectra and H NMR are given in
the supplementary material. CCDC 1007148 contains the supplementary crystallographic data.
These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html or by
application to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223
3
36 033; deposit@ccdc.cam.ac.uk.
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Table 1. Crystallographic data for [ZnP1].
Compound
[ZnP1]CH
2
Cl
2
Empirical formula
Formula weight
Temperature(K)
Wavelength(Å)
Crystal system
space group
C
54
H
39Cl
3
N
4
O
2
947.61
223(2) K
1.54178
Monoclinic
P2
a
1
/c
=
=
=
b
c
Unit cell dimensions
α = 90°
β
=
γ = 90°
4496.87(15)
3
Volume (Å )
Z
4
-
3

(g cm )
1.400
1952
F(000)
3
Crystal size(mm )
0.35 x 0.30 x
3.65° to 70.00°
Theta range for data
-
-
-
20<=h<=21
14<=k<=10
22<=l<=30
Limiting indices
Reflections collected /
19172
unique
Completeness to theta =
99.6 %
Data / restraints / parameters 8499 / 39/ 578
GOF
,wR [I﹥2σ(I)]
1.061
R1 = 0.0546
R
1
2
wR
2
= 0.1481
R
1
,wR
2
(all data)
R
1
= 0.0663
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wR
2
= 0.1596
and
Largest diff. peak and
1.035
-3
2
2 2
2
2 1/2
R
1
=(F
0
- F
c
)/F
0
, wR
2
=w(F
0
 - F
c
 ) /w(F
0
 ) ]
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Table 2. Selected bond distances (Å) for [ZnP1].
Zn(1)N(1)
Zn(1)N(3)
N(1)C(A1)
N(2)C(A3)
N(3)C(A5)
N(4)C(A7)
C(1)O(1)
2.031(2)
2.044(2)
1.372(3)
1.371(3)
1.368(4)
1.376(4)
1.202(4)
1.460(4)
Zn(1)N(2)
Zn(1)N(4)
N(1)C(A2)
N(2)C(A4)
N(3)C(A6)
N(4)C(A8)
C(1)O(2)
2.032(2)
2.034(2)
1.378(3)
1.378(3)
1.375(6)
1.371(4)
1.328(4)
1.784(8)
C(2)O(2)
C(5)Cl(1)
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1
Figure 1. H NMR spectra of B1, P1 and [ZnP1] in CDCl
3
.
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Figure 2. ORTEP diagram of [ZnP1]. The hydrogen atoms of the porphyrin have been omitted
for clarity. 50% probability ellipsoids are depicted.
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Figure 3. Formal diagrams of the porphyrinato cores for [ZnP1]. Illustrated are the
displacements of each atom from the mean plane of the 24 atom in units of 0.01 Å
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Scheme 1. Synthetic route to the compound P1 using phenols.
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Scheme 2. i) Synthetic route to P1 using dry HCl. ii) Synthetic route to B1 by using catechol. iii)
Synthetic route to B1 by using dry HCl.
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